United States Patent (19) 11 3,854,947 Ritchey (45) Dec. 17, 1974

(54) PROCESS AND SOLUTION FOR FIXING AN 57 ABSTRACT IMAGE ON SLVER HALDE PRINTS A rapid process for producing a stable visible image in 76 Inventor: Edward R. Ritchey, 303 S. 5th St., a photographic silver halide emulsion layer containing St. Joseph, Mo. 64501 a latent image which comprises developing the layer in a photographic silver halide developing solution and 22 Filed: May 16, 1973 fixing the silver halide forming the resultant image by (21) Appl. No.: 360,652 immersing the layer in a novel fixing solution. The novel fixing solution has a major proportion of a solu tion including a first compound selected from the 52) U.S. Cl...... 96/61 R, 96/50 R group consisting of alkali metal thiocyanate, ammo (51 Int. Cl...... G03c 5/38, GO3c 5/26 nium thiocyanate, alkali metal thiosulfate, and ammo 58 Field of Search...... 96/50 R, 61 R nium thiosulfate, and a minor proportion of a second (56) References Cited solution including an anionic synthetic detergent hav ing a carbon chain length in the range of between UNITED STATES PATENTS about 7 to about 18 carbon atoms per molecule and 2,343,696 31 1944. Muehler et al...... 96/61 R selected from the group consisting of ammonium lau 2,578,075 21 1951 Kienast ...... 96/61 R ryl sulfate sodium lauryl sulfate, potassium lauryl sul 2,860,978 l l l 1958 Henn et al...... 96/6 R 3, 132,943 5/1964 Smith et al...... 96/61 R fate, aklylated aromatic sulfonic acids, and mixtures thereof, and a water softening agent selected from the 3,404,004 loll 968 Ake ...... 96/50 group consisting of sodium hexametaphosphate so 3,573,912 4ll 971 Brown...... 96/61 R dium pyrophosphate, sodium tetraphosphate, and mix Primary Examiner-Mary F. Kelley tures thereof. The resultant image layer is subse Attorney, Agent, or Firm-John H. Widdowson quently rinsed in a moving water bath. 30 Claims, No Drawings 3,854,947 2 PROCESS AND SOLUTION FOR FIXNG AN process completely cleared the photographic layer of MAGE ON SILVER HALDE PRINTS all chemical residue in minimultime with a single soak, BACKGROUND OF THE INVENTION and simultaneously to soaking the process provided a flattening treatment. However, this patented process 1. Field of the Invention did not curtail the time for fixing the silver halide form This invention relates to photography. Most specifi ing the resultant latent image by immersing the layer in cally, this invention provides a rapid process for pro a thiosulfate or thiocyanate solution; nor could this ducing a stable visible image in a photographic silver process eliminate the step of stopping the action of the halide emulsion layer containing a latent image, and a developing solution by immersing the layer in an acetic novel fixing solution for use therein. O 2. Description of the Prior Art acid solution. It is generally old in the art of producing a stable visi Therefore, what is needed and what has been in ble image and photographic silver halide emulsion vented by me since Oct. 1, 1968, the date which Ake layer containing a latent image formed therein by expo U.S. Pat. No. 3,404,004 issued, is a novel process and sure to light in a camera, enlarger, X-ray machine, or 15 a new fixing solution which is to be used therein, which similar apparatuses, to develop the silver halide layer in produces a stable visible image in a photographic silver a developing solution, to stop the developing action of halide emulsion layer containing a latent image without the developer solution, to fix the silver halide forming the foregoing deficienciess associated with the prior the resultant image by immersing the layer in a stabiliz art. ing solution, and to subsequently rinse the resultant 20 SUMMARY OF THE INVENTION photographic image layer in a moving water bath. This process has been disclosed by Richard W. Henn et al It is therefore an object of this invention to provide in U.S. Pat. No. 2,860,978, patented Nov. 18, 1958, a novel process and fixing solution for producing a sta Eric T. Smith et al in U.S. Pat. No. 3,132,943, patented ble visible image in a photographic silver halide emul May 12, 1964, and in Ake U.S. Pat. No. 3,404,004, pa 25 sion layer containing a latent image which includes a tented Oct. 1, 1968. Prior to Ake patent, it was com shorter fixing time with archival permanence. mon subsequent to fixing to go through an extensive It is another object of this invention to provide a and time consuming washing operation taking approxi novel process and fixing solution for producing a stable mately from 30 minutes to 60 minutes in order to re visible image in a photographic silver halide emulsion move all fixing chemicals from the plate or print. The 30 layer containing a latent image which requires no stop removal of these fixing chemicals and soluble by bath and gives no darkroom odors. products of the fixing operation is necessary in order to It is yet another object of this invention to provide a prevent deterioration of the print, film, or plate caused new photographic processing method and a non-toxic, from residual thiosulfate or thiocyanate solutions con biodegradable fixing solution wherein there is less wash verting part of the silver image into a yellowish or 35 time and is relatively economical to manufacture and brownish silver sulfide. This extensive washing could be install in known apparatuses and processes, shortened to approximately 3 minutes, followed by im Still, other objects will be apparent to those skilled in mersion into a running water bath for 20 minutes. Even the art from the following description of this invention. the inclusion of the "hypo' eliminator step and subse The foregoing objects were achieved according to quent washing should be followed by another bath op 40 the practice of this invention. Broadly, this invention eration for flattening the print or plate; which should comprises an improved rapid process for producing a still yet be followed by still another bath to provide for stable visible image in a photographic silver halide treatment prior to handling the plate or print on an en emulsion layer containing a latent image which in larging machine, orsimilar apparatus, and in toning op cludes developing the layer in a photographic silver erations. The time consuming washing operation foll 45 halide developing solution. Subsequent to developing, lowing the hypo eliminator step normally takes from the silver halide forming the resultant latent image is between 25 to 35 minutes. Conventional processes fixed by immersing the layer in a novel fixing solution after the hypo treatment require a minimum of four having a major proportion of a solution including a first washing operations, baths, or solutions, and the equip compound selected from the group consisting of alkali ment form handling the same. Notwithstanding this rig 50 metal thiocyanate, ammonium thiocyanate, alkali orous extensive and time consuming washing, fre metal thiosulfate and ammonium thiosulfate. The novel quently a portion of the chemicals used to process the fixing solution additionally includes a minor proportion print or plate still remain and decompose to cause of a second solution including an anionic synthetic de staining. tergent having a carbon chain length in the range of be Ake U.S. Pat. No. 3,404,004, discloses a new rapid 55 tween about 7 to about 18 carbon atoms per molecule process and a final soak bath used therein for produc and selected from the group consisting of ammonium ing a stable image in a photographic layer containing a lauryl sulfate, sodium lauryl sulfate, potassium lauryl latent image which solved many of the foregoing prob sulfate, alkylated aromatic sulphonic acids, and mix lems associated with developing processes known to tures thereof, and a water softening agent selected from the prior art. This patented rapid process includes the 60 the group consisting of sodium hexametaphosphate, so steps of (1) developing the layer in a developing solu dium pyrophosphate, sodium tetraphosphate, and mix tion; (2) stopping the action of the developing solution; tures thereof. The second solution preferably addition (3) fixing the resultant image in a stabilizing solution; ally includes a print flattening agent selected from the and (4) treating the layer in the final soak bath for re 65 group consisting of propylene glycol, hexylene glycol, moving chemical residue. Following the last step, the ethylene glycol, glycerol, and mixtures thereof; and a resultant image is rinsed in a moving water bath for a defoaming agent selected from the group consisting of time interval in a range of about 4 to 7 minutes. The methylhexacarbonyl sulfonated ores, sulfonated sili 3,854,947 3 4 cones, and mixtures thereof. Following fixing, the re made from glacial acetic acid which has been diluted sultant image layer is rinsed in a moving water bath. with water in a ratio of about three parts of glacial Thus, by the practice of this invention, there is pro acetic acid with eight parts of water. Crystalline boric vided a rapid and economical process for producing a acid should be used instead of powdered boric acid be stable visible image in a photographic silver halide cause the powdered acid dissolves only with great diffi emulsion layer containing a latent image, and a novel culty. fixing solution which is used within the process. If an alkaline non-hardening bath is desired, the first Detailed Description of the Invention fixing agent compound should have a concentration in the range of between about 145 to about 175 grams per In the new rapid process of my invention, the photo O liter of water; the desiccated alkali metal sulfite or am graphic print, X-ray, plates, negatives, or other photo monium sulfite should include a concentration in the graphic elements are initially placed in a silver halide range of between about 4 to about 9 grams per liter of developing solution. The photographic elements in water; and the alkali metal bisulfite or ammonium bi general have a silver halide emulsion layer containing sulfite should possess a concentration in the range of a latent image. The latent image is formed in the emul 5 between about 12 to about 21 grams per liter of water. sion layer by exposure to light in a camera, enlarger, If the acid hardening bath is desired, then first solution X-ray machine, or similar apparatus. The developer should contain the first fixing agent with a concentra bath can be of any suitable type known to the prior art, tion in the range of between about 135 to about 160 as for example, a mild reducing agent such as pyrogallic grams per liter of water; the desiccated alkali metal sul acid. If the photographic elements are multilayer pho 20 fite or ammonium sulfite in a concentration range of tographic film, paper, etc., used for color photography between about 5 to about 15 grams per liter of water; containing three or more selectively sensitive emulsion the glacial acetic acid in a concentration range of be layers coated on a photographic support and possibly tween about 20 cc to about 40 cc per liter of water including color forming compounds or couplers, the wherein every three parts of the glacial acetic acid has developer bath or baths will be selected to develop the 25 been initially diluted with eight parts of water; crystals respective type of film or photographic element. of boric acid having a concentration range of between After the photographic element has been removed about 1 gram to about 10 grams per liter of water; and from the developer bath, or baths, it is either immersed potassium or chrome alum including a concentration directly into my novel fixing solution, or it is immersed range of between about 5 grams to about 15 grams per in a solution for stopping the action of the developer 30 liter of water. In the preferred embodiment of the in solution prior to immersing the photographic element vention, a non-hardening bath of the first solution com into the new fixing solution. The choice of steps will prises 160 grams of sodium thiosulfate per liter of wa hereinafter follow as the description and proceeds de ter, about 6.6 grams of desiccated sodium sulfite per pends upon certain concentrations of certain solutions liter of water, and about 16.7 grams of sodium bisulfite within my fixing solution which comprises a major pro 35 per liter of water. The preferred embodiment of the portion of a first solution including a first fixing agent acid hardening bath of the first solution comprises compound selected from the group consisting of alkali about 147.5 grams of sodium thiosulfate per liter of wa metal thiocyanate, ammonium thiocyanate, alkali ter, about 9.25 grams of sodium sulfite per liter of wa metal thiosulfate, and ammonium thiosulfate. The al ter, about 29.2 grams of 28% pure acetic acid per liter kali metal thiocyanate may be selected from the group 40 of water, about 4.62 grams of crystazls of boric acid per consisting of lithium thiocyanate, sodium thiocyanate, liter of water, and about 9.25 grams of potassium or potassium thiocyanate, rubidium thiocyanate, and ce chrome alum per liter of water. sium thiocyanate, and the alkali metal thiosulfate may The novel fixing solution additionally includes a be selected from the group consisting of lithium thio minor portion of a second solution including an anionic sulfate, sodium thiosulfate, potassium thiosulfate, ru 45 synthetic detergent having a carbon chain length in a bidium thiosulfate, and cesium thiosulfate. If an alka range of between about 7 to about 18 carbon atoms per line fixing solution is desired, the first solution should molecule and selected from the group consisting of am additionally include desiccated alkali metal sulfite or monium lauryl sulfate, sodium lauryl sulfate, potassium desiccated ammonium sulfite, alkali metal bisulfite or lauryl sulfate, alkylated aromatic sulfonic acid, and ammonium bisulfite and water. The desiccated alkali 50 mixtures thereof, and a water softening agent selected metal sulfite may be selected from the group consisting from the group consisting of sodium hexametaphos of desiccated lithium sulfite, sodium sulfite, potassium phate, sodium pyrophosphate, sodium tetraphosphate sulfite, rubidium sulfite, and cesium sulfite. Similarly, and mixtures thereof. Preferably, the second solution the alkali metal bisulfite may be selected from the additionally includes a print flattening agent selected group consisting of lithium bisulfite, sodium bisulfite, 55 from the group consisting offpropylene glycol, hexylene potassium bisulfite, rubidium bisulfite, and cesium bi glycol, ethylene glycol, glycerol, and mixtures thereof; sulfite. However, the first fixing agent is normally used and a defoaming agent selected from the group consist in an acid solution instead of an alkaline fixing solution ing of methylhexacarbonyl, sulfonated ores, sulfonated because the acid stops developing as quickly as it dif silicones and mixtures thereof. fuses into the film, and it also prevents oxygen oxida The detergent agent used in my second solution may tion of the developing agent with the attendant possibil be any suitable type of the detergent. By detergent it is ity of stain formation. Thus, if an acid hardening bath meant a compound having a molecule characterized as is desired in place of the alkaline non-hardening bath, a relatively large hydro carbon molecule having from then a quantity of acetic acid, crystals of boric acid, 65 7 to 18 carbon atoms, usually aliphatic or alkyl substi and potassium alum or chrome alum may be substi tuted aromatics in nature. One portion of the molecule tuted for the alkali metal bisulfite or ammonium bisul is water soluble and posesses a relatively high polarity. fite. The acetic acid is preferably 28% pure acetic acid This is the hydrophilic or solubilizing group. Typical 3,854,947 S 6 solubilizing groups are -COOH, -SO3H, and sent directly to fixing after the developing without hav -SOHRs. The most preferred detergent for use in ing to be immersed in a short solution. It has been dis the practice of my invention is ammonium lauryl sul covered that if between about 1 and 5 ounces of the fate sold under the trademark SIPON L22 by Alcolac second solution is used with about 1 gallon of a working Chemical Corporation. The detergent agent, preferably 5 solution (that which includes water) of the first solu ammonium lauryl sulfate, can be used in any suitable tion, then after developing the photographic silver hal concentration in the second solution. However, I prefer ide emulsion layer may be directly immersed for about to use the detergent in a concentration range of be 2 minutes in the fixing solution without having to be ini tween about 0.002 to about 0.02 grams per liter, more tially immersed in a short-stop solution. If more than preferably a concentration in the range of about 0.006 10 about 5 ounces of the second solution concentrate to about 0.007 grams per liter. (that which is without water) is used with about 1 gal Any suitable water softening agent can be used in the lon of a working solution of the first solution, then after second solution of my invention. The preferred water developing and in accordance with the procedures softening agent for use in the second solution of my in which are well known to those skilled in the art, the vention is hexametaphosphate, sold under the trade 15 mark Calgon by Calgon Corporation, and fully de print, plate or paper, should be placed in a short-stop scribed in U.S. Pat. No. 2,494,828. The water softening acid solution. The short-stop acid solution includes a agent, preferably hexametaphosphate, can be used in dilute solution of acetic acid having approximately be any suitable concentration in the second solution of my tween about 0.2% to about 0.8% of acetic acid, prefer invention. Preferably, the water softening agent is used ably about 0.5% of acetic acid. The immersion of the in a concentration range of between about 0.01 to photographic silver halide layer in the short-stop solu about 0.15 grams per liter; more preferably, in the tion should be from between about 15 seconds to about range of between about 0.02 to about 0.03 grams per 45 seconds, preferably 30 seconds. I have also discov liter; and most preferably, a concentration of about ered that a working solution of my second solution may 0.022 grams per liter. 25 be substituted for the short-stop acid solution. If a A print flattening agent may be included in the sec working solution of my second solution is substituted ond solution of my invention. It is preferred that the for the short-stop acid solution to stop the developing print flattening agent by propylene glycol and used in action, then the photographic silver halide emulsion the aqueous solution in any suitable concentration; layer should be immersed in my second solution from preferably in the range of between about 2.6 X 10 to 30 between about 15 seconds to about 45 seconds, and about 65 x 10 gram moles per liter; more preferably, preferably for about 30 seconds. in a concentration range of between about 4.8 x 10 In the following is set forth examples of my invention to about 9.5 x 10 gram moles per liter. A suitable de which are given by way of illustration and not by limita foaming agent may also be used in the second solution tion. The specific concentrations, temperatures, times, in the practice of my invention. The preferred defoam 35 compounds, etc. set forth in these examples are not to ing agent used in the second solution of my invention be construed to unduly limit the scope of the invention. is 2 - octanol. Another preferred defoaming agent is a EXAMPLE I sulfonated silicone mixture sold under the tradmark Antifoam B by Dow Corning Corporation. The de Four double weight thickness photographic papers foaming agent, preferably 2-octanol, may be used in 40 having a single halide emulsion layer thereon, were ex any suitable concentration. Preferably, the concentra posed to produce a latent image thereon. The papers tion is in the range of between about 0.7 x 10 to were then developed in a conventional silver halide de about 23 x 10 gram moles per liter; more preferably, veloping solution. After the papers were removed from the concentration is in range of between about 2.7 X the developing solution, the developing action of the 10 to about 5.6 X 10 gram moles per liter. 45 developing solution was stopped by immersing the pa The second solution and the first solution may be pers in an acetic acid solution. Each of the four photo mixed in any suitable concentration. Preferably, the graphic papers were subsequently fixed by a different second solution is mixed at a ratio of between about 1 method. ounce to about 20 ounces of the second solution to Method I took one of the four-photographic papers about 1 gallon to the first solution. More preferably, 50 and immersed it in a well known fixing solution of so the mixture ratio is between about 2 ounces to about dium thiosulfate hypo sold by Eastman Kodak Com 12 ounces of the second solution to about 1 gallon of pany, Rochester, N.Y., a corporation of New Jersey. the first solution; and most preferably, the mixing ratio After five minutes of being immersed in this fixing solu is between about 4 ounces to about 6 ounces of the sec tion, the paper was washed in a running water whose ond solution to about 1 gallon of the first solution. 55 temperature was 68°F. The photographic silver halide emulsion layer con Method II took another paper and following a five taining a latent image should be immersed in the novel minute fixation within the same fixing solution of fixing solution from between about 1 minute to about Method I, soaked the paper for about 3 minutes in a 5 minutes; preferably, for about 2 minutes. After im Kodak hypo eliminator. After the immersion within this mersion in the fixing solution, the photographic silver 60 eliminator solution, the paper was washed in a running halide emulsion layer should be rinsed in a moving water bath having a temperature of about 68°F. The water bath from between about 1 minute to about 20 hypo eliminator had the following composition: minutes, preferably for about 5 minutes; and subse quently dried in a normal manner which is well known Water 500cc. to those skilled in the art. 65 Hydrogen Peroxide (3% solution) 125.0 c.c. As was previously mentioned, the photographic silver Ammonia (3% solution) 100.0 c.c. halide emulsion layer containing a latent image may be Water to dilute 1.0 liter 3,854,947 7 8 The hydrogen peroxide was initially dissolved in 500 cc of water and then the remaining chemical, ammonia, TABLE was added, taking care that the hydrogen peroxide was WASHTME RESIDUAL HYPO IN mg/cm FOREACH dissolved before adding the ammonia subsequently, IN MINUES METHOD water to dilute was added to the required volume. III IV Method III took a third paper and after fixation with too high to 3 eaSle 4.5 3.3 3.3 the same fixing solution of Method I which is well 6 6. 3.4 3.1 3.5 known to those skilled in the art, soaked the paper in 10 4.2 3.3 2.6 1.0 5 4.0 3.1 25 0.9 the novel bath solution of Ake U.S. Pat. No. 3,404,004 O 25 3.3 2.4 2.3 0.5 having a concentration of about four ounces of the con 60 1.4 .0 0.6 0.4 Sumer concentrate (i.e. 4 ounces of the concentrate so lution per about 1 gallon of water) per about one gallon From the results of Table I, Method I illustrates that of water. This concentration of composition of the removal of residual hypo by simple washing was dis novel bath solution was clearly disclosed in Ake patent. 15 couragingly slow and consequently, Method I cannot After about a two minute soak in this bath solution, the possibly be considered as an effective procedure for paper was washed in a running water which had a tem hypo elimination from paper based emulsions. Methods perature of about 68°F. II and III produce almost parallel results. In each case, Method IV took the last and fourth paper and fixed 20 residual hypo content was reduced to reasonable limits a stable visible image with the novel fixing solution of within comparable times. Therefore, the choice of this invention. The fixing solution had a mixture ratio eliminaters between the one used in Method II and the of about 4 ounces of the consumer concentrate of the one in Method III cannot be made on the basis of hypo second solution to about gallon of a working solution removal rates. Both were effective with Method III of the first solution which had the following composi- 25 being the most effective after a certain specific time. tion: Method IV was the process where my novel fixing solu tion was used and is clearly the method of choice be cause the paper was fixed and effectively free of resid Water 6.5 liters ual hypo. Within 10 minutes after fixing the hypo level Sodium Thiosulfate 147.5 grams/liter of HO 30 was reduced to archivial limits (1.0 mg/cm). No elimi Desiccated Sodium Sulfate 9.25 grams/liter of HO nator bath prior to washing was necessary to accelerate Acetic Acid (28% pure) 29.2 grams/liter of HO Crystals of Boric Acid 4.62 grams/liter of HO the washing time. Also, there were no deleterious ef Potassium Alum 9.25 grams/liter of HO fects resulting from mixing of the first solution with the second solution. The sodium thiosulfate was initially dissolved in about 35 .EXAMPLE I 4.06 liters of water having a temperature of about Method IV of Example I has a short-stop solution for 125F. Then the remaining chemicals were added in stopping the developing of the conventional silver hal the order given, taking care that each chemical was ide developing solution which consist of the chemical completely dissolved before adding the next. The re 40 composition of the second solution of Example I. When maining about 2.44 liters was added to dilute the solu the tests and measurements of Method IV are repeated, tion to the required working condition. the results are similar and prove that my second solu The second solution had the following composition: tion may be substituted for a conventional short-stop acetic acid solution for stopping the developing action. 45 EXAMPLE III Ammonium lauryl sulfate 0.85 ounces A non-hardening alkaline first fixing solution has the Propylene glycol 0.05 ounces following composition: Antifoam B (Dow Corning Corporation) 0, 10 ounces Sodium hexametaphosphate (Calgon, Calgon Corporation) 3.0 ounces 50 Water 1.5 Liters Sodium thiosulfate 160 grams/liter of HO Four ounces of the concentrate solution was then Desiccated Sodium sulfite 6.6FE of HO combined with water to make a gallon of a consumer Sodium bisulfite 16.7 grams/liter of HO concentrate. About 0.5 liters of water having a temperature of Following a five minute submersion of the fourth 55 about 125F is used to initially dissolve the sodium thio paper within my fixing solution, it was washed in run sulfate. The remaining chemicals are dissolved in order ning water having a temperature of about 68°F. given, taking care that each is completely dissolved All four methods washed the paper for about 60 min prior to adding the next. The remaining about 1.0 liters utes and took sodium thiosulfate measurements at 3, 6, of water was finally added to dilute the first solution to 10, 15, 25 and 60 minutes. The apparatus used for a working condition. The second solution has the same chemical composi these measurements is well known to those in the art tion as the one given in Example I. However, in this ex and was five-dram vials with polyethylene caps and a ample, only about 4 ounces of the consumer concen Carey Spectrophotometer. Table I gives the quantita strate of the second solution are used with about 1 gal tive results of the residual hypo (sodium thiosulfate) lon of the first alkaline fixing solution. No short-stop measured in mg/cm as the aforementioned times for solution is used to stop the developing action and the each method. photographic paper is directly submerged from the de 3,854,947 9 10 veloping step into the fixing solution of this example. range of between about 0.01 to about 0.15 grams per After about 2 minutes of immersion, measurements of liter. residual hypo are taken at the specific times of Table 5. The rapid process of claim 3 wherein said print I. After 60 minutes of washing, the residual hypo meas flattening agent includes a concentration between urements are similar to the measurements of Method about 2.6 x 10 to about 65 X 10 gram moles per li IV and further illustrate that my novel manner of fixing ter, and said defoaming agent includes a concentration can eliminate hypo faster than any process known to range of between about 0.7 x 10 to about 23 x 10 the prior art. gram mole per liter. The foregoing examples illustrate that the new rapid 6. The rapid process of claim 1 wherein said immers process and novel fixing solution for processing photo 10 ing of said layer in said fixing solution is between about graphic prints of my invention take considerably less 1 minute to about 5 minutes, and said rinsing of said re time and favorable results are obtained. Upon comple sultant image in a moving water bath is between about tion of the example, it was determined that the papers 2 minutes to about 20 minutes. were in perfect condition for toning operation. Also, 7. The rapid process of claim 1 wherein said alkali the prints exhibited no apparent tendency to curl and 15 metal thiocyanate is selected from the group consisting showed less tendency to stain after drying, of lithium thiocyanate, sodium thiocyanate potassium While the present invention has been described thiocyanate, rubidium thiocyanate, and cesium thiocy herein with reference to particular embodiments anate and said alkali metal thiosulfate is selected from thereof, and specific examples, a latitude of modifica the group lithium thiosulfate, sodium thiosulfate, potas tions, various changes and substitutions are intended in 20 sium thiosulfate, rubidium thiosulfate, and cesium thio the foregoing disclosure, and in some instances some sulfate. features of the invention will be employed without a 8. The rapid process of claim 2 wherein said develop corresponding use of other features without departing ing stop solution is a dilute solution of acetic acid in from the scope of the invention as set forth. cluding approximately between about 0.2% to about I claim: 25 0.8% of acetic acid, and said immersing of said layer is 1. A rapid process for producing a stable visible from between about 15 seconds to about 45 seconds. image in a photographic silver halide emulsion layer 9. The rapid process of claim 2 wherein said develop containing a latent image, ing stop solution is of the composition of said second a. developing said layer in a photographic silver hal solution and said immersing of said layer in said devel ide developing solution, 30 oping stop solution is from between about 15 seconds b. fixing said silver halide forming the resultant image to about 45 seconds. by immersing said layer in a fixing solution having 10. The rapid process of claim 7 wherein said first so a major proportion of, (l) a first solution compris lution additionally includes desiccated alkali metal sul ing a compound selected from the group consisting fite, alkali metal bisulfite and water. of alkali metal thiocyanate, ammonium thiocya 35 11. The rapid process of claim 10 wherein said desic nate, alkali metal thiosulfate and ammonium thio cated alkali metal sulfite is selected from the group sulfate, and, (2) a minor proportion of a second so consisting of lithium sulfite, sodium sulfite, potassium lution including an anionic synthetic detergent hav sulfite, rubidium sulfite, and cesium sulfite and mix ing a carbon chain length in the range of about 7 tures thereof, and said alkali metal bisulfite is selected to about 18 carbon atoms per molecule and se 40 from the group consisting of lithium bisulfite, sodium lected from the group consisting of ammonium lau bisulfite, potassium bisulfite, rubidium bisulfite and ce ryl sulfate, sodium lauryl sulfate, potassium lauryl sium bisulfite, and mixtures thereof, sulfate, alkylated aromatic sulfonic acids, and mix tures thereof, and a water softening agent selected 12. The rapid process of claim 11 wherein a quantity from the group consisting of sodium hexameta 45 of acetic acid, crystals of boric acid and potassium phosphate, sodium pyrophosphate, sodium tetra alum are substituted for said alkali metal bisulfite. phosphate, and mixtures thereof, wherein said sec 13. The rapid process of claim 1 wherein said first so ond solution and said first solution are mixed at a lution comprises water, between about 135 to about ratio of between about 1 ounce to about 20 ounces 160 grams per liter of water of a thiosulfate solution se 50 lected from the group consisting of alkali metal thiosul of said second solution to about 1 gallon of said fate and ammonium thiosulfate, and a desiccated sul first solution, and fite solution selected from the group consisting of alkali c. rinsing the resultant image layer in a moving water metal sulfite and ammonium sulfite having a concentra bath. tion in the range of between about 5 to about 15 grams 2. The rapid process of claim 1 additionally including per liter of water, a glacial acetic acid in a concentra immersing said layer in a developing stop solution after 55 tion range of between about 20 cc to about 40 cc per developing and prior to said fixing. liter of water wherein every three parts of said glacial 3. The rapid process of claim 1 wherein said second acetic acid has been initially diluted with eight parts of solution additionally includes a print flattening agent water, crystals of boric acid having a concentration selected from the group consisting of propylene glycol, 60 range of between about 1 gram to about 10 grams per hexylene glycol, ethylene glycol, glycerol, and mixtures liter of water, and potassium alum including a concen thereof, and a defoaming agent selected from the group tration range of between about 5 grams to about 15 consisting of methylhexacarbonyl, sulfonated oils, sul grams per liter of water. fonated silicones, and mixtures thereof. 14. The rapid process of claim 3 wherein said first so 4. The rapid process of claim 1 wherein said anionic 65 lution comprises water, about 147.5 grams of sodium synthetic detergent includes a concentration between thiosulfate per liter of water, desiccated sodium sulfite about 0.002 to about 0.02 grams per liter, and said in a concentration of about 9.25 grams per liter of wa water softening agent includes a concentration in the ter, said glacial acetic acid having a concentration of 3,854,947 11 12 about 29.2 grams per liter of water, said crystals of 22. The fixing solution of claim 18 wherein said alkali boric acid having a concentration of about 4.62 grams metal thiocyanate is selected from the group consisting per liter of water, and said potassium alum having a of lithium thiocyanate, sodium thiocyanate, potassium concentration of about 9.25 grams per liter of water. thiocyanate, rubidium thiocyanate, and cesium thiocy 15. The rapid process of claim 12 wherein chrome anate, and mixtures thereof, and said alkali metal thio alum is substituted for said potassium alum. sulfate is selected from the group consisting of lithium 16. The rapid process of claim 10 wherein said first thiosulfate, sodium thiosulfate, potassium thiosulfate, solution comprises water, a thiosulfate solution se rubidium thiosulfate and cesium thiosulfate, and mix lected from the group consisting of alkali metal thiosul tures thereof. fate and ammonium thiosulfate and in a concentration 10 23. The fixing solution of claim 22 wherein said first range of between about 145 to about 175 grams per li solution additionally includes a desiccated sulfite solu ter, a desiccated sulfite solution selected from the tion selected from the group consisting of an alkali group consisting of an alkali metal sulfite and ammo metal sulfite and ammonium sulfite, and a bisulfite so nium sulfite and in a concentration range of between lution selected from the group consisting of an alkali about 4 to about 9 grams per liter of water, and a bisul 15 metal bisulfite and ammonium bisulfite. fite solution selected from the group consisting of an 24. The fixing solution of claim 23 wherein said des alkali metal bisulfite and ammonium bisulfite in a con iccated alkali metal sulfite is selected from the group centration range of between about 12 to about 21 consisting of lithium sulfite, sodium sulfite, potassium grams per liter of water. sulfite, rubidium sulfite and cesium sulfite and mixtures 17. The rapid process of claim 16 wherein said first thereof, and said alkali metal bisulfite is selected from solution comprises water, sodium thiosulfate in a con the group consisting of lithium bisulfite, sodium bisul centration of about 160 grams per liter of water, desic fite, potassium bisulfite, rubidium bisulfite, and cesium cated sodium sulfite in a concentration of about 616 bisulfite, and mixtures thereof. grams per liter of water, and sodium bisulfite having a 25. The fixing solution of claim 23 wherein a quantity concentration of about 16.7 grams per liter of water. 25 of acetic acid, crystals of boric acid and potassium 18. A fixing solution for fixing a stable visible image alum are substituted for said bisulfite solution. on a developed photographic silver halide emulsion 26. The fixing solution of claim 18 wherein said first layer, comprising: - solution comprises water, a first compound selected a, a major proportion of a first solution including a from the group consisting of alkali metal thiocyanate, first compound selected from the group consisting 30 ammonium thiocyanate, alkali metal thiosulfate and of alkali metal thiocyanate, ammonium thiocya ammonium thiosulfate, in a concentration range of be nate, alkali metal thiosulfate and ammonium thio tween about 135 to about 160 grams per liter of water, sulfate, and a desiccated sulfate solution selected from the group b. a minor proportion of a second solution including 35 consisting of alkali metal sulfate and ammonium sulfate an anionic synthetic detergent having a carbon in a concentration range of between about 5 to about 15 grams per liter of water, a glacial acid in a concen chain length in the range of between about 7 to tration range of between about 20 cc to about 40 cc per about 18 carbon atoms per molecule and selected liter of water wherein about every 3 parts of said glacial from the group consisting of ammonium lauryl sul acetic acid has been initially diluted with 8 parts of wa fate, sodium lauryl sulfate, and potassium lauryl 40 ter, crystals of boric acid having a concentration range sulfate, alkylated aromatic sulfonic acids, and mix of between about 1 gram to about 10 grams per liter of tures thereof, and a water softening agent selected water, and potassium alum including a concentration from sodium hexametaphosphate, sodium pyro range of between about 5 grams to about 15 grams per phosphate, sodium tetraphosphate, and mixtures liter of water. thereof, wherein said second solution and said first 45 27. The fixing solution of claim 26 wherein said first solution are mixed at a ratio of between about 1 solution comprises water, sodium thiosulfate in a con ounce to about 20 ounces of said second solution centration of about 147.5 grams per liter of water, des to about 1 gallon of said first solution. iccated sodium sulfate in a concentration of about 9.25 19. The fixing solution of claim 18 wherein said sec grams per liter of water, said glacial acetic acid in a ond solution additionally includes a print flattening 50 concentration of about 29.2 grams per liter of water, agent selected from the group consisting of propylene crystals of boric acid having a concentration of about glycol, hexylene glycol, ethylene glycol, glycerol, and 4.62 grams per liter of water, and potassium alum hav mixtures thereof, and a defoaming agent selected from ing a concentration of about 9.25 grams per liter of wa the group consisting of methylhexacarbonyl, sulfonated ter. oils, sulfonated silicones and mixtures thereof. 55 28. The fixing solution of claim 25 wherein chrome 20. A fixing solution of claim 18 wherein said anionic alum is substituted for said potassium alum. synthetic detergent includes a concentration in the 29. The fixing solution of claim 24 wherein said first range of between about 0.002 to about 0.02 grams per solution comprises water, a thiosulfate solution se liter, and said water softening agent includes a concen lected from the group consisting of alkali metal thiosul tration in the range of between about 0.01 to about fate and ammonium thiosulfate and having a concen 0.15 grams per liter. tration in the range of between about 145 to about 175 21. The fixing solution of claim 19 wherein said print grams per liter of water, a desiccated sulfite solution flattening agent includes a concentration in the range selected from the group consisting of an alkali metal of between about 2.6 x 10 to about 65 X 10 gram 65 sulfite and ammonium sulfite in a concentration range moles per liter, and said defoaming agent includes a of between about 4 to about 9 grams per liter of water, concentration in the range of about 0.7 X 10 to about and a bisulfite solution selected from the group consist 23 X 10 gram moles per liter. ing of alkali metal bisulfite and ammonium bisulfite in 3,854,947 13 14 a concentration range of between about 12 to about 21 cated sodium sulfite in a concentration of about 6.6 grams per liter of water. grams per liter of water, and sodium bisulfite in a con solution30. The comprises fixing solution water, of sodium claim 29thiosulfate wherein insaid a con-first centration of about 16.76 grams per literli off water. centration of about 160 grams per liter of water, desic- 5 sk xk k x xk

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65 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,854,947 Dated December 17, 1974 Inventor(s) Edward R. Ritchey It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Column 5, line 28, delete "by" and insert therefor -- be --. Column 7, line 3l, delete "Sulfate" and insert therefor -- Sullifite -- . line 66, delete "as" and insert therefor -- at --. Column 10, line 63, delete "3" and insert therefor -- 13 --.

Signed and sealed this l8th day of arch l975.

(SEAL) Attest : C, ARSAE.L. DANN(, try RUTH C & O Conrnissioner of Fatents Attesting Officer and Trademarks

RM po- 1050 (10-69) USCOMMedC 537 6aeeg U.S. GoWERNMEN PRNTING office: 869. 930